4 Turbite solid elimination

4.1 Theory
About 80 % of all wastewater constituents, measured e.g. in BOD, exist in a suspended
colloidal structure. Hence, all basic processes, which remove suspended substances, are of
great significance (e.g. flocculation, sedimentation, flotation, filtration, etc.). The process of
flocculation, which always played a major role in water supply systems as well as in
treatment of industrial wastewater, will become more important because of its exceptional
flexibility, easy controlling, monitoring and eventual mechanization capabilities. The great
flexibility of flocculation processes arises from the large number of existing flocculation
agents, which can be applied to remove specific substances, from the variation of the energy
input, and allocated reaction time, etc.

The efficiency of such processes depends on the chemical composition of the wastewater,
the surface chemistry of the colloidal particle, the hydrodynamics of the system, the extend of
the interaction between the soluble and insoluble wastewater constituents as well as the
hydrolyzing metal salts used as flocculation agents.

Flocculation is generally the process that transfers suspended substances, which exist in
water in a colloidal from, to larger agglomerates. These “flocks” reach a physical state and
size that allows it to sediment, to float or to be filtered. This state makes it possible to
separate the suspension form water.

The point of view to divide the flocculation process in two immediately succeeding single
processes has been successfully established over the past time in the field of water
chemistry. These two processes are:

Flocculation = destabilization + transport processes

The first step of the process eliminates the opposing forces, which inhibit the coming closer
respectively, unification of the evenly distributed colloidal particles in water. This means that
the disperse system is “destabilized“ and makes the agglomeration of the particle possible.
This process happens very fast (a few seconds) if the corresponding flocculation agent is
added and the solution is mixed quickly, whereas the succeeding transport process needs
more time to build flocks with increasing size.

The following Table (Tab. 4.1) gives a schematic overview of flocculation and precipitation on
one hand as well as the different partial flocculation processes on the other hand.
Tab. 4.1: Overview of the mechanisms of precipitation and flocculation

Flocculation Destabilization Transport

Coagulation compression of the electrical peri-kinetic

double layer with counter (Browns movement)
ions d<1 µm 2nd order reaction

reduction of the surface ortho-kinetic

potential (velocity gradient)
d>1 µm 1st order reaction

Flocculation forming of molecular bonds

(macromolecules, poly-ions,
poly-electrolytes)

Precipitation encapsulation and dragging

colloidal particles in
voluminous precipitation
products

Destabilization

Coagulation:

Dispersed colloidal particles in water have an enveloping double-layer of ions because of

their electrostatic surface property. Since the particles are equally charged they repulse each
other (see Fig. 4.1). By adding ions of opposite charge the electrostatic surface charge (zeta-
potential) of the suspended particles decreases and the proceeding agglomeration (collision)
and flock growth can take place.
repulsive energy

repulsive term

ea
0

distance between particles

attractive energy

curve for the resulting interactive energy

attractive term

-200

Fig. 4.1: Influence of the particle distance on the interaction energy

The reduction of the repulsing charges is based on the fact that the high zeta-potential with a
low ion concentration is decreased strongly when increasing the ion concentration (see Fig.
4.1). One must differentiate between the effect of higher charged, non hypolisierenden ions
- 4.2 -
with their coagulation effect depending on the size and charge of the ion and the effect of
hypolisierenden ions where their higher charged products of hydrolysis hold an additional
charge which is attracted and absorbed by electrostatic oppositely charged colloidal
particles.

These two processes are called electrolytic coagulation (unspecific coagulation) and in the
second case, adsorptive coagulation (specific coagulation).

Flocculation:

The destabilization of the colloidal suspension happens by the interlacing and meshing of the
finest particles through bounds, which are formed by linear chain molecules. These synthetic
organic polymers so called “flocculation agents” enable, because of their large shape, the
union of finest dispersed particles to larger agglomerates without having to significantly
decrease their zeta-potential. If these chain molecules posses groups with ionic character
they are called polyelectrolytes.

Fig. 4.2: Example for a cathodic poly-electrolyte

a) Structure of a cathodic poly-electrolyte (polyvinylpyridin)

b) Schematic representation of a cathodic poly-electrolyte in an aqueous solution

Transport

Once the system is destabilized the transport process is necessary to induce as many
collisions of the particles as possible. This enables the forming of always growing
agglomerates until they reach a size where they can be easily separated from the aqueous
phase.

The building of micro flocks, caused by the Brown molecular motion, so called perikinetic
flocculation is not sufficient for the existing separation systems. To obtain the desired size of
the flocks input of energy from the outside is necessary to stimulate a relative motion
between the particles. The velocity gradient of each particle must be chosen in such a
manner that the ratio of flock creating collision frequency and the flock destructive shear
force is optimal so that the most possibly compacted flocks are formed. Once the swift
destabilizing process, with a reaction time of about 30 min., has taken place this so called
orthokinetic flocculation process is the process-determining step for practical applications.

- 4.3 -
Design of flocculation systems

The methods to design flocculation systems for wastewater treatment are manly transferable
from today’s water processing technology. To produce a large and compact flock with good
sedimentation properties, it is necessary for the particles to collide and unify very frequently
to form larger agglomerates.

The velocity gradient that directly determines the collision frequency must not increase the
simultaneously occurring shear forces above the physical durability (shear strength) of the
flocks. For practical purposes a simple formulation for the forming of flocks

rB = k 1 C G (4.1)
with k1 = forming velocity coefficient for flock
C = flock concentration
G = velocity gradient

and for the destruction of flocks

rB = k2 Gm (4.2)
with k2 = demoliting velocity coefficient for flock
m = empiric exponent (often m = 2) proven

More detailed conceptions of the flocculation model can be read in the literature of
Smoluchowski, 1916 and 1918.

As a parameter that significantly influences flocculation the velocity gradient G is to be

determined. The theoretical derivation is only possible for very simple flow conditions. It is
not possible to mathematically describe the flow in a flocculation reactor normally used in a
practical application. The following formulation has been proven successful to produces a
valid approximation, also for “calculable systems”.

P
G= (4.3)
VR η
with P = power input
VR = reactor volume
η = dynamic viscosity

When designing a flocculation reactor apart from the ideal chemical dosage the size of the
reactor and its performance are to be determined in terms of the stirrer speed. Table 4.2
shows some typical values for the different parameters.

- 4.4 -
Tab. 4.2: recommended values for flocculation systems

Parameter Symbol Unit Pre-mixer Flocculation

reactor
Reaction time tR s 10 to 60 600 to 1800
Velocity G s-1 300 10 to 100
gradient

Energy input GtR; Ca - - 6*103 to 2*105

value
(Camp value)
Capacity P/VR W m-3 100 0,1 to 10
-3 -4 -3
Energy P/VR tR kWh m 3*10 to 2*10 2*10-5 to 5*10-3
expense
Revolution of n min-1
stirrer:
propeller stirrer 150 to 1500
turbine stirrer 15 to 150
paddle stirrer - 2 to 15
Tangential vT m s-1 0,2 to 1
velocity of
paddle stirrer
Paddle surface % 10 to 20
vs. reactor
cross section
Flow rate in vX m s-1 0,25 to 0,4
the flocculation
reactor

Mixing systems for the flocculation process

Figure 4.3 schematically shows different devices, which reliably work for fast as well as soft
stirring.

- 4.5 -
 flocculant

effluent effluent

influent

influent
A. turbine B. propeller
rotor

stator

C. paddle mixer

effluent
influent effluent

inflow

vertical redirection horizontal redirection

D. redirected flow
Fig. 4.3: Different devices for the mixing process for flocculation

More clues to design flocculation devices are gained through modification of known
apparatuses form water processing systems.

For wastewater flocculation the destabilization theory or stoichiometry can not be used to
determine the interaction between flocculation agents and wastewater in advance. To
determine the sum of all the influencing factors in the flocculation process several
experiments, the so-called JAR-test, must be conducted in advance. In six beakers, using a
common stirring system, the flocculation process with the subsequent sedimentation is
simulated and continuously monitored via sampling. The cross-section of the device shown
in Fig. 4.4 is used for the phosphate precipitation in wastewater treatment plants as well as in
water processing plants. It is especially used to determine the optimal precipitation agents
dosage and combination.

- 4.6 -
Fig. 4.4: Experimental apparatus for flocculation (Jar-test)

Literature

Von Smoluchowski, M.: Drei Vorträge über Diffusion, Brownsche Molekularbewegung und
Koagulation von Kolloidteilchen. Physikalische zeitschrift, 17, S. 557ff, 1916.

Von Smoluchowski, M.: Versuch einer mathematischen Theorie der Koagulationskinetik

kolloidaler Lösungen. Zeitschrift für physikalische Chemie, 92, S. 129ff, 1918.

Hahn , H.H. (Hsgb.): Fortschritte bei der Anwendung von Flockungsverfahren in der
Abwassertechnologie. ISWW, Uni Karlsruhe , Band 20, 1979.

Hahn , H.H. (Hsgb.): Schlämme aus der Abwasserfõllung/-flockung. ISWW , Uni Karlsruhe,
Band 32, 1983.

Walther , H.-J.; Winkler , F.: Wasserbehandlung durch Flockungsprozesse. Akade-

mie-Verlag Berlin, 1981.

- 4.7 -
 4.2 Turbidity measurement
To judge the quality of flocculation the number of particles in suspension must be measured.
This is very intensive process. The turbitity measurement has been proven to work very well
for practical applications as a value of the particle concentration and is therefore found again
in the norms (DIN 38404, part 2). Two procedures are used:

1. degradation measurement (weakening) of passing light

2. light scattering measurement

4.2.1 Degradation measurement of passing light

The spectral degradation coefficient µ(λ) is determined at a fixed wavelength (usually 620
nm) using commercial photometers. First, set the photometer to zero using “aqua dest”
solution. Second, measure the extinction of the probe. To calculate the spectral weakening
coefficient use the following equation:

E
µ(λ) = (4.4)
d
 I 
with E = Extinction  Def. : E = − log 
 I0 
d = layer thickness of cuvette
The light fraction absorbed should not be large otherwise the spectral degradation coefficient
is an inappropriate measure for the particle content. The spectral degradation coefficient
consists of two parts:

µ(λ) = s(λ) + a(λ) (4.5)

with s(λ) = spectral light dispersion coefficient
a(λ) = spectral absorption coefficient
To determine the spectral light dispersion coefficient s(λ),first the spectral absorption
coefficient of a filtered sample has to be determine and subtracted form the spectral
degradation coefficient.

4.2.2 Measuring the light dispersion

At low turbidities the measurement of the dispersed light is suitable. To measure this
dispersion a dispersion light meter is used. A beam of white light is directed at the sample
and the dispersed light is measured at an angle of 90°, therefore the absorption of the water
itself can be neglected. To calibrate the dispersion light meter the turbidity of a standard
solution of Formazin is measured. Values obtained in this manner are stated in turbidity
units, referring to the calibration with Formazin (abbreviation: TU/F).

Foramzin is not commercially available because its durability is limited. First the following two
solutions are to be mixed:

Solution 1: 10,0 g of Hexamethyltetramine, C6H12N4, are dissolved in aqua dest; the solution
is filled up to 100 ml with aqua dest.

- 4.8 -
Solution 2: 1,0 g of Hydraziniumsulfate, N2H6SO4, is dissolved in aqua dest; the solution is
also filled up to 100 ml with aqua dest.

5 ml of solution 1 is mixed with 5ml of solution 2 and filled up to 100 ml with aqua dest after
standing for 24h at a temperature of 25 ± 3 °C. The turbidity coefficient of this solution is 400
TE/F. Using aqua dest a series of blanks at suitable concentrations have to be prepared.
The turbidity limit for discharge into natural waters is usually 10 TF/F.

4.3 Performing the measurement

Here we want to flocculate a model suspension where the turbidity limit of 10 TU/F is not
exceeded and the flocculated sludge has good sedimentation properties. The same
substances are used for flocculation as previously discussed in the introducing chapter. The
concentration of chemicals as well as the number of revolutions when stirring is to be varied
for flocculation. Figure 4.5 shows the flocculation test device, which is used in this
experiment. This machine allows stirring fore batches simultaneously. It is important to keep
the pH between 5 to 6.

Chemical agent
dosage

Figure 4.5: Experimental set up for the estimation of chemical agent dosage

The success is evaluated by measuring the turbidity. First, we have to prepare a calibration
line. The necessary standards are supplied in the lab. Second, the samples have to be
measured using a turbidity photometer. The signals are then converted into TU/F units.

The sedimentation properties of flocculation sludge is evaluated using the following

parameters:

- 4.9 -
1. Sedimentation velocity vs

Fill 100 ml of the sludge suspension into a lockable graduate cylinder and shake it well.
After some time the sludge level is sinking. Record the change of the sludge level with
respect to time. Figure 4.6 shows a typical sedimentation curve. The slope of the linear
section of the curve gives the sedimentation velocity of the sludge.

2. Sludge volume Vs

After 30 min the sedimentation process of the sludge in the graduate cylinder is
complete. Now we can determine the volume of the compressed sludge and compare it
to the total volume (100 ml).

3. Sludge index ISV

To calculate the sludge volume index the sludge volume Vs is divided by the sludge
concentration CTS. The sludge concentration can be measured like described in chapter 2
or by considering the utilization of iron salts for flocculation. The sludge volume index
measures the sludge sedimentation properties. The following is valid:

ISV < 100 ml/g : good sedimentation properties

100 > ISV < 160 ml/g : moderate sedimentation properties
ISV > 160 ml/g : poor sedimentation properties

30

25
sludge level h [cm]

20 -v S vS = 1.9 cm/min

15

10

0
0 2 4 6 8 10 12 14 16 18 20
time t [min]

Figure 4.6: Change of the sludge level with respect to time

4.4 Evaluation
Use the provided millimeter paper sheets to construct the calibration curve to determine the
turbid substance concentration as well as determining the sedimentation velocity.

The experimental results are to be recorded on the attached table.

- 4.10 -
quantity unit exper. 1.1 exper. 1.2 exper. 1.3 exper. 1.4

cFl mg/l

tFl min

nFl min-1

cCoa mg/l

tCoa min

nCoa min-1

initial cturbidity TU/F

final cturbidity TU/F

vS m/h

VS,30 ml/l

IVS ml/g

quantity unit exper. 2.1 exper. 2.2 exper. 2.3 exper. 2.4

cFl mg/l

tFl min

nFl min-1

cCoa mg/l

tCoa min

nCoa min-1

initial cturbidity TU/F

final cturbidity TU/F

vS m/h

VS,30 ml/l

IVS ml/g

- 4.11 -
quantity unit exper. 3.1 exper. 3.2 exper. 3.3 exper. 3.4

cFl mg/l

tFl min

nFl min-1

cCoa mg/l

tCoa min

nCoa min-1

initial cturbidity TU/F

final cturbidity TU/F

vS m/h

VS,30 ml/l

IVS ml/g

quantity unit exper. 4.1 exper. 4.2 exper. 4.3 exper. 4.4

cFl mg/l

tFl min

nFl min-1

cCoa mg/l

tCoa min

nCoa min-1

initial cturbidity TU/F

final cturbidity TU/F

vS m/h

VS,30 ml/l

IVS ml/g

- 4.12 -